Unit13 Plymer synthesis
chemicalreactionengineering3ededition作者octavelevenspiel课后习题答案
Corresponding Solutions for Chemical Reaction EngineeringCHAPTER 1 OVERVIEW OF CHEMICAL REACTION ENGINEERING .......................................... 错误!未定义书签。
CHAPTER 2 KINETICS OF HOMOGENEOUS REACTIONS ........................................................ 错误!未定义书签。
CHAPTER 3 INTERPRETATION OF BATCH REACTOR DATA ..................................................... 错误!未定义书签。
CHAPTER 4 INTRODUCTION TO REACTOR DESIGN ............................................................... 错误!未定义书签。
CHAPTER 5 IDEAL REACTOR FOR A SINGLE REACTOR........................................................... 错误!未定义书签。
CHAPTER 6 DESIGN FOR SINGLE REACTIONS ....................................................................... 错误!未定义书签。
CHAPTER 10 CHOOSING THE RIGHT KIND OF REACTOR ....................................................... 错误!未定义书签。
材料科技英语第一章part 2 unit 13
Part Ⅱ
polymers
Polysaccharides—多聚糖
淀粉（Starch） 菊糖（Lnulin） 树胶（Gums） 粘液（Mucilages） （多糖）由10个以上单糖分子缩合而 成，大多为无定形化合物，分子量较大， 水解后生成单糖或低聚糖
Part Ⅱ
polymers
Polypeptides —多肽
Part Ⅱ
polymers
Biological synthesis There are three main classes of biopolymers: polysaccharides,聚糖 polypeptides聚肽, and polynucleotides聚核苷酸. In living cells, they may be synthesized by enzyme-mediated processes, such as the formation of DNA catalyzed by DNA polymerase聚合酶.
Part Ⅱ
polymers
In 1922, Hermann Staudinger proposed that polymers consisted of long chains of atoms held together by covalent bonds, an idea which did not gain wide acceptance for over a decade and for which Staudinger was ultimately awarded the Nobel prize. Work by Wallace Carothers in the 1920s also demonstrated that polymers could be synthesized rationally from their constituent monomers.
聚合反应工程基础(全套课件567P)
1.1.1 高分子化合物的分类和命名
2. 结构系统命名法：由（International Union of Pure and Applied
Chemistry, IUPAC）提出
I 26
1.1.2 高分子化合物的基本特点
H--NH(CH2)6NH--CO(CH2)4CO--OH
重复结构单元
结构单元
结构单元
n
例2：尼龙66 的重复单元与结构单元
----( CH2--CH=CH--CH 2 -)--(-CH --CH-)---2 y x
n
例3：丁苯橡胶 的重复结构单元与结构单元
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1.1.2 高分子化合物的基本特点
实际上，分子量的大小并无明确的界限，一般
-- -- - --< 1,000 < - - - - - - < 10,000 < - - - - - < 1,000,000 < - - - - 低分子物 低/齐聚物 （Oligomer） 高聚物 (Polymer)
PS
PVC PTFE PAA PET
polystyrene
Polyvinyl chloride Polytetrafluoroethylene polyacrylic acid polyester
聚甲基丙烯酯 甲酯
聚醋酸乙烯 聚乙烯醇 聚丁二烯 聚丙烯腈
PMMA
PVAc PVA PB PAN
polymethylmet hacrylate
主要参考书目
1. 陈甘棠著，《聚合反应工程基础》，中国石化出版社，1991 2. 史子瑾主编，《聚合反应工程基础》，化学工业出版社， 1991 3. C.McGreavy(Ed),“Polymer Reactor Engineering”,Blackie
主链含均三嗪环Ｄ-π-Ａ型共轭聚合物的合成及发光性能
第３９卷第６期２０２１年１１月贵州师范大学学报（自然科学版）ＪｏｕｒｎａｌｏｆＧｕｉｚｈｏｕＮｏｒｍａｌＵｎｉｖｅｒｓｉｔｙ（ＮａｔｕｒａｌＳｃｉｅｎｃｅｓ）Ｖｏｌ．３９．Ｎｏ．６Ｎｏｖ．２０２１引用格式：肖尊宏．主链含均三嗪环Ｄ π Ａ型共轭聚合物的合成及发光性能［Ｊ］．贵州师范大学学报（自然科学版），２０２１，３９（６）：５７ ６１．［ＸＩＡＯＺＨ．ＳｙｎｔｈｅｓｉｓａｎｄｌｕｍｉｎｅｓｃｅｎｃｅｐｒｏｐｅｒｔｉｅｓｏｆＤ π Ａｔｙｐｅｃｏｎｊｕｇａｔｅｐｏｌｙｍｅｒｉｎｍａｉｎｃｈａｉｎ［Ｊ］．ＪｏｕｒｎａｌｏｆＧｕｉｚｈｏｕＮｏｒｍａｌＵｎｉｖｅｒｓｉｔｙ（ＮａｔｕｒａｌＳｃｉｅｎｃｅｓ），２０２１，３９（６）：５７ ６１．］主链含均三嗪环Ｄ π Ａ型共轭聚合物的合成及发光性能肖尊宏（贵州师范大学化学与材料科学学院，贵州贵阳 ５５００２５）摘要：用乙腈和无水乙醇合成了三甲基均三嗪，然后依次与正丁醛、对苯二甲醛缩合反应，首次制备了主链含均三嗪环Ｄ π Ａ型共轭聚合物；用红外光谱、紫外光谱和氢谱对共轭聚合物进行了表征，确定是所需要的目标聚合物。
该聚合物在３６０ｎｍ紫外光的激发下，发出５９７ｎｍ较强的纯正红光，是一种潜在的白光聚合物电致发光器件所需要的红光材料。
关键词：电致发光；聚合物；红光材料中图分类号：Ｘ５０２；Ｏ６３１ 文献标识码：Ａ 文章编号：１００４—５５７０（２０２１）０６－００５７－０６ＤＯＩ：１０．１６６１４／ｊ．ｇｚｎｕｊ．ｚｒｂ．２０２１．０６．０１１ＳｙｎｔｈｅｓｉｓａｎｄｌｕｍｉｎｅｓｃｅｎｃｅｐｒｏｐｅｒｔｉｅｓｏｆＤ π ＡｔｙｐｅｃｏｎｊｕｇａｔｅｐｏｌｙｍｅｒｉｎｍａｉｎｃｈａｉｎＸＩＡＯＺｕｎｈｏｎｇ（ＳｃｈｏｏｌｏｆＣｈｅｍｉｓｔｒｙａｎｄＭａｔｅｒｉａｌｓ，ＧｕｉｚｈｏｕＮｏｒｍａｌＵｎｉｖｅｒｓｉｔｙ，Ｇｕｉｙａｎｇ，Ｇｕｉｚｈｏｕ５５００２５，Ｃｈｉｎａ）Ａｂｓｔｒａｃｔ：Ｔｒｉｍｅｔｈｙｌ ｓ ｔｒｉａｚｉｎｅｗａｓｓｙｎｔｈｅｓｉｚｅｄｗｉｔｈａｃｅｔｏｎｉｔｒｉｌｅａｎｄａｂｓｏｌｕｔｅｅｔｈｙｌａｌｃｏｈｏｌｆｉｒｓｔｌｙａｎｄＤ π Ａｔｙｐｅｃｏｎｊｕｇａｔｅｐｏｌｙｍｅｒ（Ｐ）ｃｏｎｔａｉｎｉｎｇｓ ｔｒｉａｚｉｎｅｗａｓｐｒｅｐａｒｅｄｂｙｃｏｎｄｅｎｓａｔｉｏｎｒｅａｃｔｉｏｎｗｉｔｈｂｕｔｙｒａｌｄｅｈｙｄｅａｎｄｐｈｔｈａｌａｌｄｅｈｙｄｅｓｕｃｃｅｓｓｉｖｅｌｙ．ＴｈｅｃｏｎｊｕｇａｔｅｐｏｌｙｍｅｒｗａｓｃｈａｒａｃｔｅｒｉｚｅｄｂｙＩＲ，ＵＶａｎｄ１ＨＮＭＲａｎｄｃｏｎｆｉｒｍｅｄｔａｒｇｅｔｐｏｌｙｍｅｒ．Ｔｈｅｃｏｎｊｕｇａｔｅｐｏｌｙｍｅｒｅｍｉｔｔｅｄｐｕｒｅｓｔｒｏｎｇｅｒｒｅｄｌｉｇｈｔａｔ５９７ｎｍｗｈｅｎｅｘｃｉｔｅｄｂｙ３６０ｎｍＵＶｌｉｇｈｔ．ＩｔｉｓｐｏｔｅｎｔｉａｌｒｅｄｍａｔｅｒｉａｌｏｆＷＰＬＥＤ（ｗｈｉｔｅｐｏｌｙｍｅｒｌｉｇｈｔｅｍｉｔｔｉｎｇｄｉｏｄｅ）．Ｋｅｙｗｏｒｄｓ：ｅｌｅｃｔｒｏｌｕｍｉｎｅｓｃｅｎｃｅ；ｐｏｌｙｍｅｒｓ；ｒｅｄｌｉｇｈｔｍａｔｅｒｉａｌｓ０ 引言自从１９７７年Ｃｈｉａｎｇ等［１］发现导电聚乙炔以来，共轭聚合物在电致发光器件（Ｐ ＬＥＤ）、太阳能电池（ＰＳＣｓ）、能源转换等方面的应用前景引起了许多科学家的兴趣，成为新的研究热点［２－６］。
polymer chemistry分区
polymer chemistry分区聚合物化学是研究聚合物合成、结构和性质的学科。
聚合物是由重复单元组成的大分子化合物，可以广泛应用于生活中的各个领域。
本文将聚合物化学分为三个方向进行讨论，分别是聚合物合成、结构和性质。
一、聚合物合成聚合物合成是指通过化学反应将单体转化为聚合物的过程。
这个过程可以通过不同的方法来实现，包括添加剂聚合、步骤聚合和自由基聚合等。
添加剂聚合是指在聚合过程中添加引发剂和其他添加剂，以控制聚合反应的速率和聚合物的分子结构。
步骤聚合是指通过多步反应逐渐合成聚合物，每一步反应都有特定的条件和反应物。
自由基聚合是最常见的聚合方法，它利用自由基引发剂引发聚合反应，从而生成聚合物。
二、聚合物结构聚合物的结构对其性能和用途起着重要的影响。
聚合物的结构可以分为线性结构、支化结构和交联结构等。
线性聚合物是由直线状的聚合物链组成，具有良好的可塑性和可拉伸性。
支化聚合物是指在聚合物链上引入支链，增加了聚合物的分子间交错程度，改善了聚合物的熔融性和热稳定性。
交联聚合物是指在聚合物链之间形成交联结构，使聚合物具有良好的机械性能和耐热性能。
三、聚合物性质聚合物的性质是指聚合物在特定条件下表现出的物理和化学特性。
聚合物的性质包括力学性能、热性能、电性能和光学性能等。
力学性能是指聚合物的强度、韧性和硬度等，这些性能决定了聚合物在工程领域的应用。
热性能是指聚合物的熔点、玻璃化转变温度和热分解温度等，这些性能决定了聚合物在高温条件下的稳定性。
电性能是指聚合物的导电性和绝缘性，这些性能决定了聚合物在电子器件和电气设备中的应用。
光学性能是指聚合物对光的吸收、透射和散射等特性，这些性能决定了聚合物在光学领域的应用。
聚合物化学是一个综合性的学科，涉及到聚合物的合成、结构和性质等方面。
通过深入研究聚合物化学，可以为开发新型聚合物材料和改良现有聚合物材料提供理论基础和技术支持，推动聚合物材料的发展和应用。
中英文工程术语对照表
11A-basis A基准：在采用材料之机械性质时，其值必统计值所预测之落点有95%之可信度Abhesive 离型膜ABL Bottle ABL瓶Ablate 摩擦，磨损Ablation 切除，削磨Ablative plastic 耐磨塑料Abrasion 摩擦，磨损Absolute rate constant 绝对速率常数in anionic chain polymerization 阴离子链聚合反应之绝对反应速率常数in cationic chain polymerization 阳离子链聚合反应之绝对反应速率常数in coordination polymerization 配位聚合反应之绝对反应速率常数in radical chain polymerization 自由基链聚合反应之绝对反应速率常数in ring-opening polymerization 开环聚合反应之绝对反应速率常数in step polymerization 逐步聚合反应之绝对反应速率常数Accelerator 促进剂，加速剂Acetylene polymerization 炔属聚合反应Acidity function 酸性作用，酸性功能Acousic 音响学的Acousic Microscopy 音学显微检测仪Acrolein polymerization 丙烯醛聚合反应Acrylamide polymerization 丙烯醯胺聚合反应Actinometry 光量测定Activated monomer 经催化单体，经活化单体Activation 催化，活化Activation Energy 活化能in anionic chain polymerization 阴离子链聚合反应之活化能in cationic chain polymerization 阳离子链聚合反应之活化能in coordination polymerization 配位聚合反应之活化能in radical chain polymerization 自由基链聚合反应之活化能in ring-opening polymerization 开环聚合反应之活化能in step polymerization 逐步聚合反应之活化能Activator 催化剂，活化剂Activity of catalyst 触媒之活性Addition polymer 加成聚合物Addition polymerization 加成聚合反应Additive 填充剂Adherend 黏着剂、附着Adhesion 黏着Adhesive 胶料，黏着剂Adhesive film 黏着膜Adhesive Shear 黏着剪力强度Adhesiveness 黏着性Advanced composite 高级复合材料After-affect technique 后效应技术After Bake 后硬化，同post-cureAggregate 集合体Aging 老化，材料受环境影响（物理、化学）而Air-Bubble Void 气泡孔Air-drying of alkyds 醇酸之空气干燥法Air Lock 气闸Air Vent 排气孔AirworthinessAligned discontinuous fiber 与Long discontinuous fiber (简称LDF 维。
化学化工专业英语电子版课本.
ContentPART 1 Introduction to Materials Science &Engineering 1 Unit 1 Materials Science and Engineering 1 Unit 2 Classification of Materials 9 Unit 3 Properties of Materials 17 Unit 4 Materials Science and Engineering: What does the Future Hold? 25 PartⅡMETALLIC MATERLALS AND ALLOYS 33 Unit 5 An Introduction to Metallic Materials 33 Unit 6 Metal Manufacturing Methods 47 Unit 7 Structure of Metallic Materials 57 Unit 8 Metal-Matrix Composites 68 PartⅢCeramics 81 Unit 9 Introduction to Ceramics 81 Unit 10 Ceramic Structures —Crystalline and Noncrystalline 88 Unit 11 Ceramic Processing Methods 97 Unit 12 Advanced ceramic materials –Functional Ceramics 105 PARTⅣNANOMATERIALS 112 Unit 13 Introduction to Nanostructured Materials 112 Unit14 Preparation of Nanomaterials 117 Unit 15 Recent Scientific Advances 126 Unit 16 The Future of Nanostructure Science and Technology 130 PartⅤPOLYMERS 136 Unit17 A Brief Review in the Development of Synthetic Polymers 136 Unit18 Polymer synthesis: Polyethylene synthesis 146 Unit19 Polymer synthesis:Nylon synthesis 154 Unit 20 Processing and Properties Polymer Materials 165 PART VI POLYMERIC COMPOSITES 172 Unit21 Introduction to Polymeric Composite Materials 172 Unit22 Composition, Structure and Morphology of Polymeric Composites 178Unit23 Manufacture of Polymer Composites 185 Unit24 Epoxy Resin Composites 191 Part 7 Biomaterial 196 Unit 25 Introduction to Biomaterials 196 Unit 26 Biocompatibility 205 Unit 27 Polymers as Biomaterials 213 Unit 28 Future of Biomaterials 224 PARTⅧMaterials and Environment 237 Unit29 Environmental Pollution & Control Related Materials 237 Unit30 Bio-degradable Polymer Materials 241 Unit 31 Environmental Friendly Inorganic Materials 248 Unit 32 A Perspective on the Future: Challenges and Opportunities 256 附录一科技英语构词法263 附录二科技英语语法及翻译简介269附录三:聚合物英缩写、全名、中文名对照表280 附录四:练习题参考答案284 PART 1 Introduction to Materials Science &EngineeringUnit 1Materials Science and Engineering Historical PerspectiveMaterials are probably more deep-seated in our culture than most of us realize. Transportation, housing, clothing, communication, recreation, and food production —virtually every segment of our everyday lives is influenced to one degree or another by materials. Historically, the development and advancement of societies ha ve been intimately tied to the members‘ ability to produce and manipulate materi- als to fill their needs. In fact, early civilizations have been designated by the level of their materials development (Stone Age, Bronze Age, Iron Age.The earliest humans had access to only a very limited number of materials, those that occur naturally: stone, wood, clay, skins, and so on. With time they discovered techniques for producing materials that had properties superior to those of the natural ones; these new materials included pottery and various metals. Furthermore, it was discovered that the properties of a material could be altered by heat treatments and by the addition of other substances. At this point, materials utilization was totally a selection process that involved deciding from a given, rather limited set of materials the one best suited for an application by virtue of its characteristics.①It was not until relatively recent times that scientists came to understand the relationships between the structural elements of materials and their properties. This knowledge, acquired over approximately the past 100 years, has empowered them to fashion, to a large degree, the characteristics of materials. Thus, tens of thousands of different materials have evolved with rather specialized charac- teristics that meet the needs of our modern and complex society; these include metals, plastics, glasses, and fibers. deep-seated根深蒂固的, 深层的pottery / ☐☯❑♓陶器structural elements结构成分;property / ☐❑☐☜♦♓/⏹.性能The development of many technologies that make our existence so comfortable has been intimately associated with the accessibility of suitable materials. An advancement in the understanding of a material type is often the forerunner to the stepwise progression of a technology. For example, automobiles would not havebeen possibl- e without the availability of inexpensive steel or some other comparable substitute. In our contemporary era, sophisticated electronic devices rely on components that are made from what are called semiconducting materials. Materials Science and EngineeringThe discipline of materials science involves investigating the relationships that exist between the structures and properties of materials. In contrast, materials engineering is, on the basis of these structure–property correlations, designing or engineering the structure of a material to produce a predetermined set of properties.―Structure‘‘ is at this point a nebulous term that deserves some explanation. In brief, the structure of a material usually relates to the arrangement of its internal components. Subatomic structure involves electrons within the individual atoms and interactions with their nuclei. On an atomic level, structure encompasses the organization of atoms or molecules relative to one another. The next larger structural realm, which contains large groups of atoms that are normally agglomerated together, is termed‗‗microscopic,‘‘ meaning that which is subject to direct observation using some type of microscope. Finally, structural elements that may be viewed with the naked eye are termed ‗‗macroscopic.‘‘The notion of ‗‗property‘‘ deserves elaboration. While in service use, all materials are exposed to external stimuli that evoke some type of response. For example, aspecimen subjected to forces will experience deformation; or a polished metal surface will reflect light. Property is a material trait in terms of the kind and magnitude of response to a specific imposed stimulus. Generally, definitions of properties are made independent of material shape and size.Virtually all important properties of solid materials may be grouped into six different categories: mechanical, electrical, thermal, magnetic, optical, and stepwise /♦♦♏☐♦♋♓/ ♎逐步的sophisticated/♦☯♐♓♦♦♓♏♓♦♓♎/ ♎精制的,复杂的; semiconducting materials 半导体材料nebulous/ ⏹♏♌✞●☯♦/♎含糊的,有歧义的subatomic/ ♦✈♌☯❍♎亚原子的microscopic/❍♓❑☯☐♓♎微观的❍♋♍❑☐♦♍☐☐♓♍/❍✌❑☯✞☐♓♎宏观的deteriorative. For each there is a characteristic type of stimulus capable of provokingdifferent responses. Mechanical properties relate deformation to an applied load or force; examples include elastic modulus and strength. For electrical properties, such as electrical conductivity and dielectric constant, the stimulus is an electric field. The thermal behavior of solids can be represented in terms of heat capacity and thermalconductivity. Magnetic properties demonstrate the response of a material to the application of a magnetic field. For optical properties, the stimulus is electro- magnetic or light radiation; index of refraction and reflectivity are representative optical properties. Finally, deteriorative characteristics indicate the chemical reactivity of materials.In addition to structure and properties, two other important components are involved in the science and engineering of materials, viz. ‗‗processing‘‘ and‗‗performance.‘‘ With regard to the relationships of these four components, the structure of a material will depend on how it is processed. Furthermore, a material‘s perf ormance will be a function of its properties.Fig. 1.1 Photograph showing the light transmittance of three aluminum oxide specimens. From left to right: single crystal material (sapphire, which is transparent;a polycrystalline and fully dense (nonporous material, which is translucent; and a polycrystalline material that contains approximately 5% porosity, which is opaque. (Specimen preparation, P. A. Lessing; photography by J. Telford.We now present an example of these processing-structure-properties-perfor- mance principles with Figure 1.1, a photograph showing three thin disk specimens placed over some printed matter. It is obvious that the optical properties (i.e., the deformation/♎♓♐❍♏♓☞☯变形deteriorative/♎♓♓☯❑♓☯❑♏♓♦♓破坏(老化的elastic modulus 弹性模量strength /♦♦❑♏⏹♑强度;dielectric constant介电常数;heat capacity 热容量refraction/❑♓♐❑✌☞☯折射率; reflectivity/ ❑♓♐●♏♓♓♦♓/ 反射率processing/☐❑☯◆♏♦♓☠加工light transmittance of each of the three materials are different; the one on the left is transparent (i.e., virtually all of the reflected light passes through it, whereas the disks in the center and on the right are, respectively, translucent and opaque.All of these specimens are of the same material, aluminum oxide, but the leftmost one is what we call a single crystal—that is, it is highly perfect—which gives rise to its transparency. The center one is composed of numerous and verysmall single crystals that are all connected; the boundaries between these small crystals scatter a portion of the light reflected from the printed page, which makes this material optically translucent.②And finally, the specimen on the right is composed not only of many small, interconnected crystals, but also of a large number of very small pores or void spaces. These pores also effectively scatter the reflected light and render this material opaque.Thus, the structures of these three specimens are different in terms of crystal boundaries and pores, which affect the optical transmittance properties. Furthermore, each material was produced using a different processing technique. And, of course, if optical transmittance is an important parameter relative to the ultimate in-service application, the performance of each material will be different.Why Study Materials science and Engineering?Why do we study materials? Many an applied scientist or engineer, whether mechanical, civil, chemical, or electrical, will at one time or another be exposed to a design problem involving materials. Examples might include a transmission gear, the superstructure for a building, an oil refinery component, or an integrated circuit chip. Ofcourse, materials scientists and engineers are specialists who are totally involved in the investigation and design of materials.Many times, a materials problem is one of selecting the right material from the many thousands that are available. There are several criteria on which the final decision is normally based. First of all, the in-service conditions must be charac- terized, for these will dictate the properties required of the material. On only rare occasions does a material possess the maximum or ideal combination of properties. transmittance/♦❑✌❍♓♦☜⏹♦/ ⏹. 透射性sapphire /♦✌♐♓☯蓝宝石transparent/♦❑✌☐☪☯❑☯⏹♦/ ♎透明的;polycrystalline/ ☐♓❑♓♦♦☯♓多晶体; translucent/♦❑✌✞♎半透明的; opaque☯✞☐♏♓♎不透明的single crystal 单晶体Thus, it may be necessary to trade off one characteristic for another. The classic example involves strength and ductility; normally, a material having a high strength will have only a limited ductility. In such cases a reasonable compromise between two or more properties may be necessary.A second selection consideration is any deterioration of material properties that may occur during service operation. For example, significant reductions in mecha- nical strength may result from exposure to elevated temperatures or corrosive envir- onments.Finally, probably the overriding consideration is that of economics: What will the finished product cost? A material may be found that has the ideal set of proper- ties but is prohibitively expensive. Here again, some compromise is inevitable.The cost of a finished piece also includes any expense incurred during fabrication to produce the desired shape. The more familiar an engineer or scientist is with the various characteristics and structure–property relationships, as well as processing techniques of materials, the more proficient and confident he or she will be to make judicious materials choices based on these criteria.③Reference:William D. Callister, Materials science and engineering : anintroduction, Press:John Wiley & Sons, Inc.,2007;2-5 transmission gear传动齿轮dictate/♎♓♏♓决定trade off 权衡;折衷ductility♎✈♓●♓♦♓延展性/ ☯✞☯❑♋♓♎♓☠/♎最主要的judicious/♎✞✞♎♓☞☯♦/♎明智的Notes1.At this point, materials utilization was totally a selection process that involved deciding froma given, rather limited set of materials the one best suited for an application by virtue of itscharacteristics由此看来,材料的使用完全就是一个选择过程,且此过程又是根据材料的性质从许多的而不是非有限的材料中选择一种最适于某种用途的材料。
高分子化学中英文
几何异构 Geometrical Isomerism
凝胶点 Gel point, Pc
凝胶效应 Gel Effect
凝胶化 Gelation
玻璃化温度 Glass Transition Temperature, Tg
接枝聚合 Graft Copolymerization
链节 Chain Element
链引发 Chain Initiation
连锁聚合 Chain Polymerization
链增长 Chain Propagation
链终止 Chain Termination
链转移 Chain Transfer
链转移剂 Chain Transfer Agent
中英文对照
加聚反应 Addition Polymerization
加聚物 Addition Polymer
粘结剂 Adhesive
老化 Ageing
交替共聚物 Alternating Copolymer
元素有机高分子 Elementary Organic Polymer
乳化作用 Emulsification
乳化剂 Emulsifier
乳液聚合 Emulsion Polymerization
乳胶粒 Emulsion Particle
对映体异构 Enantiomer Isomerism
合成高分子 Synthetic Polymer
遥爪聚合物 Telechelic Polymer
涤纶 Terylene or Poly(ethylene terephthalate), PET
JOURNAL OF POLYMER SCIENCE PART A, POLYMER CHEMISTRY 2013, 51, 229–240
Tunable Fluorescence Conjugated Copolymers Consisting of Tetraphenylethylene and Fluorene Units:From Aggregation-Induced Emission Enhancement to Dual-Channel Fluorescence ResponseJianbing Shi,1Yanmei Wu,1Shu Sun,1Bin Tong,1Junge Zhi,2Yuping Dong11School of Materials Science and Engineering,Beijing Institute of Technology,Beijing100081,China2School of Chemistry,Beijing Institute of Technology,Beijing100081,ChinaCorrespondence to:J.Shi(E-mail:bing@)or Y.Dong(E-mail:chdongyp@)Received12July2012;accepted6September2012;published online28September2012DOI:10.1002/pola.26377ABSTRACT:A series of new conjugated polymers PTPE x F y, which consist of tetraphenylethylene(TPE)units and fluorene (F)units,have been designed and synthesized by Suzuki cross-coupling polymerization.The polymers PTPE x F y exhibited aggregation-induced emission enhancement and dual-channel fluorescence response(DCFR)when they were aggregated in solution,and these properties are related with their TPE-to-F ratio in the polymer backbone.For PTPE and PTPE0.5F0.5,the fluorescence emission was enhanced by aggregation when water was added into their THF solutions.For the copolymers PTPE0.3F0.7,PTPE0.2F0.8,and PTPE0.1F0.9,the DCFRs were observed when they were aggregated by adding water into their solution,which can be attributed to the different responses of fluorene segments and TPE segments to aggrega-tion.The fluorene segments have an aggregation-caused quenching characteristic,whereas the TPE segments have an aggregation-induced emission characteristic.According to the fluorescence lifetime and quantum yield data of the polymer solutions,we have discovered that the polymer’s natural life time increases as its TPE content increases.In the solid film, PTPE0.3F0.7and PTPE0.2F0.8showed better quantum yield than other polymers,due to the combination of the excellent fluo-rescent property of the fluorene groups and the nonplanar con-formation of the TPE groups.V C2012Wiley Periodicals,Inc. J Polym Sci Part A:Polym Chem51:229–240,2013KEYWORDS:aggregation-induced emission enhancement (AIEE);conjugated polymer;copolymerization;dual-channel fluorescence response(DCFR);fluorene;luminescence;tetra-phenylethylene(TPE)INTRODUCTION Conjugated polymers(CPs)have found a wide utility in a variety of applications such as electronics,1–3 optoelectronics,4–7and sensory materials.8–11Because of their rigid conformation,they have a high tendency to aggregate both in solution and in solid state.Such aggregation leads to the dissipation of excitation energy and ultimately limits their practical applications in the aforementioned fields.Several methods have been developed to increase the quantum effi-ciency of the CPs by overcoming aggregation,for instance,by attaching large flexible side chains or branched polyionic side chains to suppress aggregation of the polymer chains,12–14or by incorporating a sterically hindered repeat unit(RU)into the CPs backbone to form a slightly twisted polymer struc-ture and hence reduce aggregation.15,16However,side chain modifications generally result in large interpolymer separa-tions that can reduce the charge and energy transfer between main chains.Incorporating iptycene units into CP main chains can effectively prevent interchain p–p interactions without isolating the chains;however,the synthesis of iptycene deriv-atives is time-consuming and requires multiple steps.Nonpla-nar propeller-shaped luminogens such as hexaphenylsilole were synthesized in2001,17,18and their light emissions can be turned‘‘on’’by aggregation formation.That is,the silole derivatives were nonemissive in dilute solutions but became highly luminescent when their molecules were aggregated in concentrated solutions or cast into solid films.This unusual fluorescence phenomenon was termed as‘‘aggregation-induced emission’’(AIE)by Tang and coworkers.17The novel AIE systems can successfully solve the quenching problem when luminescence needs to be used at high concentrations, even in solid state.Since then,a series of AIE and aggrega-tion-induced emission enhancement(AIEE)materials have been synthesized and their optoelectronic and biological applications have been explored.19–21However,most of the reported works focus on designing new small organic mole-cules or oligomers,and fully conjugated AIE or AIEE poly-mers are still rarely reported.22–24Among the AIE luminogens,tetraphenylethene(TPE)deriva-tives have been extensively studied because of its facile syn-thesis,easy functionalization,and high fluorescence quantumAdditional Supporting Information may be found in the online version of this article. V C2012Wiley Periodicals,Inc.yield.25–28In our recently published work,29we synthesized a water-soluble cationic conjugated polyelectrolyte contain-ing TPE by quaternization of its neutral CP precursor with trimethylamine.The synthesized conjugated polyelectrolyte showed AIEE phenomena upon titration of heparin into its aqueous solution.Because copolymerization of TPE and phenyl groups into conjugated main chains can retain the AIEE feature of TPE,it is intriguing to explore if copolymer-ization of other larger planar aromatic groups can also retain AIEE and if the fluorescence can be tuned by copoly-merizing TPE and other planar aromatic groups at different ratios.In this regard,we chose fluorene as the construction unit because it has well conjugated,planar,and rigid aro-matic ring structure and has high fluorescent quantum yields as well as excellent thermal and chemical stability.30 In this work,we synthesized fully conjugated copolymers by copolymerizing fluorene and TPE units at different feed ratios,as shown in Scheme1,and the copolymers showed fluorescent light-up or dual-channel response in aggregate states.Because fluorene has a typical aggregation-caused quenching(ACQ)characteristics and TPE is a typical AIE-active molecule,the obtained CPs with different fluorene and TPE units showed a novel optical behavior when they are aggregated by adding nonsolvent into their THF solu-tions.A typical AIEE phenomenon was observed for PTPE that only consists of TPE units and for PTPE0.5F0.5that consists of alternating TPE and fluorene units.In contrast, dual-channel fluorescent response was observed for PTPE0.3F0.7,PTPE0.2F0.8,and PTPE0.1F0.9that have differ-ent TPE-to-fluorene ratios.One of these signals is attributed to the fluorene emission showing ACQ-characteristics,and the other is attributed to the TPE emission showing AIEE-characteristics.RESULTS AND DISCUSSIONPolymer Synthesis and CharacterizationScheme2shows the synthetic routes of polymers PTPE and PF.The monomer2,1,2-di[4-(6-bromohexyloxy)phenyl]-1,2-di[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]ethy-lene,was synthesized in24.5%yield by heating a mixture of 1,2-di[4-(6-bromohexyloxy)phenyl]-1,2-di(4-bromophenyl)-ethylene(1)and bis(pinacolato)diboron with potassium acetate in dioxane at85 C for22h.Then,the standard pal-ladium-mediated Suzuki cross-coupling reaction between1 and2provided the neutral polymer PTPE in93.8%yield. In comparison with PTPE,the typical ACQ-characteristic polymer PF was synthesized by standard Suzuki cross-cou-pling polymerization between2,7-dibromo-9,9-bis(6-bromo-hexyl)fluorene(3)and2,2’-[9,9-bis(6-bromohexyl)-9H-fluo-rene-2,7-diyl]bis(4,4,5,5-tetramethyl)-1,3,2-dioxaborolane (4)in94.4%yield.The number-average molecular weight (M n)and polydispersity were4200and1.95for PTPE and 4300and3.04for PF,respectively,determined by gel-per-meation chromatography(GPC)system equipped with a RI detector(GPC/RI)using THF as the solvent and polystyrene as the standard.The apparently low M n values of PTPE and PF may have resulted from a technical problem in calibrat-ing the GPC system with the linear polystyrene standard. Hence,the absolute M w values of PTPE and PF were more accurately measured by using a GPC system equipped with RI,low(7 )and right(90 )angle laser light scattering detectors(GPC/RI/LALLS/RALLS),which as anticipated gave significantly higher values of PTPE and PF than the polystyrene calibration method(for comparison,M n was listed in Table1).Clearly,the Suzuki cross-coupling poly-merization of monomers1and2(or3and4)can produce soluble CPs with high molecular weights,which is consist-ent with the high yields.To obtain conjugated copolymers with different TPE-to-fluorene ratios in the backbone, copolymerization of1,4,and3at different feed ratios afforded the CPs PTPE0.5F0.5,PTPE0.3F0.7,PTPE0.2F0.8,and PTPE0.1F0.9in95.2%,94.0%,93.6%and95.2%yields, respectively,as shown in Scheme3.Their M n as well as pol-ydispersity(in parentheses)are6700(2.74),8100(4.64), 16100(5.09),and6500(4.50),respectively,as determined by GPC/RI system.These values are also small except for PTPE0.2F0.8,which are inconsistent with their highyields. Chemical structures of PTPE x F y.SCHEME2Synthetic routes of PTPE and PF.Hence,we also used GPC/RI/LALLS/RALLS to measure theirabsolute molecular weights,which gave the M n values ofPTPE0.5F0.5,PTPE0.3F0.7,PTPE0.2F0.8,and PTPE0.1F0.9to be21,700,11,500,3,64,000,and16,900,respectively.Theseresults indicate that the copolymerization of three monomerscan yield the expected CPs with satisfactory molecular weights. According to our experimental results,the reactivity of3and4is better than that of1and2because copolymeriza-tion between1and2requires a long time(30h)to giveideal CPs under the same experimental conditions.However,if the reaction time went beyond16h,the copolymerizationbetween3and4would give insoluble CPs.Therefore weattempted to tune the feed ratios of1,4,and3and prolongedthe reaction time as long as the resultant copolymers couldstill be soluble in a common solvent,and the results were veri-fied by1H NMR spectroscopy for the copolymers PTPE0.3F0.7,PTPE0.2F0.8,and PTPE0.1F0.9,as shown in Figure1.In TPE,the resonance peaks of the methylene protons attached to thephenoxy group(Ph-OC H2A)and bromine atom(A C H2Br)are located at about3.9ppm and3.4ppm,respectively.In con-trast,the methylene protons next to the bromine atom in thefluorene unit(A C H2Br)have resonance peaks at about 3.3ppm.As the TPE content in the feed decreased,the peak inten-sity at3.9ppm gradually decreased(Fig.1).Therefore,the ra-tio of TPE unit(N TPE)to fluorene unit(N F)in the copolymerscan be calculated by the following equation:N TPE=N F¼A3:9=A3:3(1) where A3.9and A3.3are the integrated areas of the proton resonance peaks at d3.9and3.3,respectively.The calculated compositions(N TPE/N F)of the copolymers are close to the TPE-to-fluorene feed ratios due to the high yields of PTPE0.3F0.7,PTPE0.2F0.8,and PTPE0.1F0.9,as summarized in Table1,indicating that the copolymer compositions can be controlled by using appropriate reaction conditions.TABLE1Characterization of PTPE x F y:Molar Ratio of Repeat Units(MRRU),Molecular Weight,and Polydispersity Indices aPolymer MRRU in theFeed(TPE:F)MRRU as Determinedby1H NMR(TPE:F)RI e LLS fYield(%)M n M w/M n M n M w/M nPTPE b100:0100:04200 1.9513,900 1.6193.8 PTPE0.5F0.5c50:5050:506700 2.7421,700 2.3995.2 PTPE0.3F0.7c30:7030.0:70.08100 4.6411,500 2.7394.0 PTPE0.2F0.8c20:8019.6:80.416,100 5.0936,4000 2.3493.6 PTPE0.1F0.9c10:9010.5:89.56500 4.5016,900 1.8695.2 PF d0:1000:1004300 3.0413,100 1.6394.4a Carried out in the mixture of toluene and aqueous solution of K2CO3(2 M)under argon at95 C using Pd(PPh3)4as catalyst.b Reaction time is30h.c Reaction time is24h.d Reaction time is16h.e Estimated by a GPC system equipped with a RI detector on the basis of polystyrene calibration.f Estimated by a GPC system equipped with RI and two-angle laser light scattering(LLS)detectors.Synthetic routes of PTPE0.5F0.5,PTPE0.3F0.7,PTPE0.2F0.8and PTPE0.1F0.9.FIGURE11H NMR spectra of PTPE x F y in CDCl3.Thermal PropertiesThe thermal properties of PTPE x F y were evaluated by ther-mogravimetric analysis(TGA)and differential scanning calo-rimetry(DSC)under nitrogen at a heating rate of10 C minÀ1.The degradation temperatures(T d)for5%weight loss and the glass transition temperatures(T g)are listed in Table2.Their corresponding TGA and DSC curves are shown in Figures S1and S2(Supporting Information).All copoly-mers are thermally stable;their T d values range from296to 312 C and have negligible differences.Obviously,the ther-mal degradation process can be divided into two stages according to the TGA curves.It is known that the aromatic groups have relatively higher thermal stability than the flexi-ble alkyl groups;31therefore,the first degradation stage is mainly attributed to the decomposition of side chains in the polymers,whereas the second degradation stage is basically attributed to the decomposition of the polymer backbone.As Table2shows,compared with PF,all copolymers containing TPE units showed higher T g in the range of90.0–111.6 C. TPE groups can obstruct the sliding process of the molecule, which decreases the free volume and elevates the T g val-ues.32No crystallization exotherms were observed during the cooling process,which indicates that all these polymers are amorphous.High T g values and noncrystalline morphol-ogy are advantageous for getting uniform and defect-free thin films because the polymers can stably stay in their glassy state without crystallization,which can be critical to optoelectronic devices.Optical PropertiesThe UV–vis absorption and photoluminescence(PL)spectra of PTPE x F y in THF solution and solid films are shown in Figures 2and3,respectively,which are normalized for comparison. The spectral data are summarized in Table3.The polymer concentration is based on RU,which includes x mol of 1,2-di[4-(6-bromohexyloxy)phenyl]-1,2-di(4-phenyl)ethylene, y mol of9,9-bis(6-bromohexyl)fluorene,where x and y are actual values calculated from1H NMR in Table1(hereinafter the same).As shown in Figure2(a),the absorption spectrum of PTPE has two peaks centered at276and367nm,corre-sponding to the p–p*transition of benzene rings and TPE seg-ments,respectively.All other polymers only show one peak, i.e.,at376,378,383,379,and382nm for PTPE0.5F0.5, PTPE0.3F0.7,PTPE0.2F0.8,PTPE0.1F0.9,and PF,respectively, which correspond to the p–p*transition of fluorene-TPE or fluorene segments.Additionally,the absorption spectrum of PTPE0.5F0.5has a broad shoulder from280to360nm,due to the p–p*transition of the benzene rings of TPE because it has the highest TPE content among four copolymers.A simi-lar characteristic was observed for the PTPE0.5F0.5film[see Fig.3(a)].The normalized PL spectra of polymers with exci-tation wavelength of380nm are shown in Figure2(b).Both PTPE and PTPE0.5F0.5show an emission peak at522nm and516nm,respectively,corresponding to the fluorescence of TPE or TPE-fluorene segments.Both PTPE0.3F0.7and PTPE0.2F0.8have two characteristic emission peaks,one cor-responding to the fluorescence of TPE-fluorene segments (515nm for PTPE0.3F0.7and506nm for PTPE0.2F0.8)andTABLE2Thermal Properties of PTPE x F yPolymer T d( C)a T g( C)bPTPE30196.1PTPE0.5F0.5298107.3PTPE0.3F0.730693.8PTPE0.2F0.8312111.6PTPE0.1F0.929690.0PF30280.0a Tdwere measured by TGA at a temperature of5%weight loss for thepolymers.b Tgwere determined by DSC on the second heatingcycle.FIGURE2Normalized UV–vis absorption(a)and PL(b)spectra of PTPE x F y at[RU]¼10l M in THF(Excitation at380nm).the other corresponding to the fluorescence of fluorene seg-ments(416nm for PTPE0.3F0.7and417nm for PTPE0.2F0.8).Because of its low TPE content in the back-bone,PTPE0.1F0.9no longer shows the fluorescence peak attributed to TPE-fluorene segments and its PL spectrum is similar to that of PF.The comparison of the PL spectra of these polymers in solution shows that the PL properties of PTPE x F y can be tuned by changing the TPE-to-fluorene molar ratio of the copolymer.The maximum UV–vis absorption wavelength(k max)in the thin films follows a similar trend compared to their dilute solutions[Fig.3(a)].However,the bandwidth is slightly broadened,as listed in Table3,perhaps due to the formation of ground state aggregates by interchain p–p*interactions that increases the effective conjugation within the mole-cule.32Moreover,the k max in the film exhibits a little blue shift for all polymers.For example,there is a10nm blue shift in the k max of PTPE0.5F0.5,which is the largest blue shift among these polymers.Other polymers have blue shifts ranging from2to6nm.The blue shift may have originated from the decreased coplanarity due to the increased disor-dered agglomeration,because spin-coating is a fast precipita-tion process that gives little time for the polymers to adjust conformation and arrange each other regularly.The PL spec-tra of all polymer films except PF also have a similar blue shift(Table3),but the emission spectra of the films are dif-ferent from those of the dilute solutions.There is only one emission peak for all polymer films,as shown in Figure3(b). The disappearance of the emission of fluorene segments in the films of PTPE0.3F0.7,PTPE0.2F0.8,and PTPE0.1F0.9is probably due to(1)self-quenching in the solid state of fluo-rene segments and(2)induced energy transfer from fluo-rene segments to TPE segments.The fluorescence lifetime(s)and quantum yield(U)are the most important characteristics of a fluorophore.To quantita-tively evaluate copolymers’emission,we investigated the fluorescence lifetime of PTPE,PTPE0.5F0.5,PTPE0.3F0.7, PTPE0.2F0.8,PTPE0.1F0.9,and PF in THF solution and infilm, FIGURE3Normalized UV–vis absorption(a)and PL(b)spectra of PTPE x F y in thin film(Excitation at380nm).TABLE3Optical Properties of PTPE x F yAbsorption k max(nm)Emission k max(nm)Peak Half-Width cW h(nm)Molar Absorptivity e max(Â107cm2/mol)Polymer Solution a Film b Solution a Film b Solution Film Solution a PTPE276,367272,364522514–d–d 2.15 PTPE0.5F0.5376366516511116126 2.28 PTPE0.3F0.7378377515,4165047178 1.52 PTPE0.2F0.8383377506,4174946275 1.92 PTPE0.1F0.93793774174946271 2.15PF3823804174505766 2.43a[RU]¼10l M in THF.b Spin-coated from5.0mg/mL THF solution.c Peak width at half peak height in the UV–vis absorption curves.d No data available.respectively.Moreover,PL quantum yields in their THF solu-tion were obtained by using quinine sulfate in0.1M H2SO4 (quantum yield¼0.55)as a standard.The absolute PL quantum yields of their films were measured by using an integrating sphere.All data are summarized in Table4.The PL quantum yields of PTPE,PTPE0.5F0.5,PTPE0.3F0.7, PTPE0.2F0.8,PTPE0.1F0.9,and PF in solution are0.016, 0.023,0.037,0.051,0.269,and1.0,respectively.The poly-mers containing TPE unit in the backbone have lower quan-tum yield than PF.THF is a good solvent for all polymers. The phenyl groups in the TPE units,which are conjugated to the emissive main chains,can freely rotate via the single-bond axes to serve as a relaxation channel for the excited state to decay.Therefore,the photonic energy is consumed by nonradiative relaxation through the amplifying effect on the conjugated main chain.This is in well agreement with the fact that most AIE-characteristic compounds usually have a lower fluorescence quantum yield in their good solvents.33 The lifetimes of PTPE,PTPE0.5F0.5,PTPE0.3F0.7,PTPE0.2F0.8, PTPE0.1F0.9,and PF in solution are 2.274, 1.648, 1.824, 1.737,1.397,and0.155ns,respectively,as measured by the fluorescence lifetime spectrometer.The homopolymer PTPE has the longest fluorescence lifetime,whereas PF has the shortest lifetime.The copolymers PTPE0.5F0.5,PTPE0.3F0.7, PTPE0.2F0.8,and PTPE0.1F0.9have similar lifetimes ranging from1.397to1.824ns.The fluorescence quantum yield is the ratio of the number of photons emitted to the number of photons absorbed.The emissive rate of the fluorophore (k f)and its rate of nonradiative decay to S0(k nr)both depopulate the excited state.The fraction of fluorophores that decays through emission,and hence the quantum yield, is given byU¼k f=k fþk nrðÞ(2) For convenience,we have grouped all possible nonradiative decay processes with the single rate constant k nr.The life-time of the excited state is defined by the average time the molecule spends in the excited state before its return to the ground state,which is expressed ass¼1=k fþk nrðÞ(3) According to eqs2and3,k f and k nr can be calculated by the experimental data of U and s.The results are listed in Table 4.It is clear that the higher fraction of fluorene in the copol-ymer in THF solution would generally result in larger k f, which greatly favors fluorescence emission.These calculation results agree well with the experiments:PTPE is weakly emissive,whereas PF is strongly emissive in solution.The lifetime of the fluorophore in the absence of nonradiative processes is called the intrinsic(or natural)lifetime,and is given bys n¼1=k f(4) Accordingly,the natural lifetime s n can be calculated from k f. The calculated values are also listed in Table5.The natural lifetime increases linearly with the increase in TPE contents, as shown in Figure4,whereas the measured lifetime shows no linearity with TPE fractions.These results indicate that incorporation of TPE into fluorene segments can indeed intrinsically alter the emissive characteristics,but other external factors such as interaction with the solvent or oxy-gen could also greatly affect the ultimate emission.In the solid film,the measured lifetime ranges from0.145to 0.439ns and is very different from that in solution.TheTABLE4The Lifetime and Quantum Yield of PTPE x F y in Solution and FilmLifetime s(ns)Quantum Yield U(%)Radiative Ratek fÂ108(sÀ1)Nonradiative Ratek nrÂ108(sÀ1)Polymer Solution a Film b Solution a,c Film b,d Solution a Film b Solution a Film b PTPE 2.2740.145 1.632.70.0703622.55 4.32746.42 PTPE0.5F0.5 1.6480.147 2.328.30.139619.25 5.92848.78 PTPE0.3F0.7 1.8240.341 3.742.60.202812.49 5.28016.84 PTPE0.2F0.8 1.7370.318 5.135.80.293611.26 5.46320.19 PTPE0.1F0.9 1.3970.39226.918.7 1.926 4.770 5.23220.74 PF0.1550.439100 1.664.520.3645022.41a[RU]¼10l M in THF.b Spin-coated from5.0mg/mL THF solution.c Quantum yield is estimated using quinine sulfate(U¼55%in0.1M H2SO4)as the standard.d Quantum yield is the absolute quantum value measured by using an integrating sphere.TABLE5The Natural Lifetime Calculated from the Emissive Rate of the Fluorophore(k f)Natural Lifetime s n(ns) Polymer Solution FilmPTPE142.1260.443 PTPE0.5F0.571.6330.519 PTPE0.3F0.749.3100.800 PTPE0.2F0.834.0600.888 PTPE0.1F0.9 5.192 2.096 PF0.15527.434lifetime of PTPE in film is shortened by up to 15times,whereas that of PF film is prolonged to three times of its lifetime in solution.The quantum yields of PTPE,PTPE 0.5F 0.5,PTPE 0.3F 0.7,PTPE 0.2F 0.8,PTPE 0.1F 0.9,and PF in film are 0.327,0.283,0.426,0.358,0.187and 0.016,respec-tively.The quantum yield of PTPE 0.3F 0.7is the highest among these polymers in film,indicating that it has the opti-mum ratio of TPE incorporation into polyfluorenes for resist-ing fluorescence quenching.The value of k f in film gradually decreases with the increasing fraction of fluorene in the co-polymer,which is detrimental to fluorescence emission.Among all polymer films,PTPE 0.3F 0.7has the minimum k nr value.The TPE molecule has a propeller shape and the fluo-rene molecule has a planar geometry.As a result,PTPE tends to adopt a twisted conformation whereas PF tends to maintain a planar conformation.In the solid state,the twisted conformation can effectively prevent p –p stacking and reduce excimer formation.Thus,the optimal TPE-to-fluo-rene ratio can enhance light emission,because fluorene seg-ments have excellent emissive properties in molecular state and TPE segments have the best emission in solid state.According to the obtained results,the optimal TPE-to-fluo-rene ratio is approximately between 3/7and 2/8.AIE PropertiesAs discussed above,the PL behaviors of these polymers in solution and in solid state are vastly different.Because the obtained polymers are easily soluble in common organic sol-vents such as dichloromethane,chloroform,THF,and DMF,their aggregation could be investigated by adding nonsolvent into their solutions.Water is the best choice because it is a nonsolvent for the polymers and the environment-friendly solvent for research.The AIE behavior was investigated by monitoring the changes in PL intensity with the addition of increasing amounts of water in a THF-water solvent mixture.PTPE has shown some AIE effect,because it has a low quan-tum yield when molecularly dissolved in its good solvent and a much improved quantum yield when aggregated in its solid state.We investigated the PL behaviors of PTPE by adding water into its THF solution.The resultant mixtures are visually transparent and macroscopically homogeneous,suggesting that the polymer aggregates have nanometer size.34When excited at 380nm,the fluorescence emission of PTPE in dilute THF solution is weak,indicating that PTPE is a weak emitter when it is molecularly dissolved.However,the PL emission intensity centering at $520nm increases proportionally upon addition of water into the solution under same measurement conditions,as shown in Figure 5(a).Because water is a nonsolvent for PTPE ,the polymer chains must be aggregated in the THF/water mixture with increased water fraction.PTPE is thus induced to emit strongly by aggregate formation;in the other words,it is indeed AIEE-active.The photographs in Figure 6clearly demonstrate the weak and strong emissions of the molecular and aggregated PTPE ,respectively.When the water fraction was increased to 90%,the emission intensity of PTPE reached maximum,which is 19times higher than that of the THF solution.Similar PL behavior was also observed for PTPE 0.5F 0.5,as shown in Figure 5(b).This phenomenon should be attributed to the following facts.First,even after the incorporation of TPE unit into the conjugated backbone of PTPE and PTPE 0.5F 0.5,its phenyl rings in the side-chains can still rotate to some extent in solution,which decays the excitation energy.Second,the intramolecular rotation is par-tially restricted in the aggregate state,which blocks the non-radiative processes of the polymers and enhances the emis-sion intensity.35In comparison to PTPE and PTPE 0.5F 0.5,the emission spec-tra of PTPE 0.3F 0.7,PTPE 0.2F 0.8,and PTPE 0.1F 0.9show two distinct peaks,one of which centering at $415nm attributed to fluorene emission and the other centering at $510nm attributed to TPE emission.Upon addition of water into their THF solution,the intensity of the fluorene emission peak decreased,whereas the intensity of the TPE emission peak increased,as shown in Figure 5(c–e).When the fraction of water reached up to 50%,the emission at 415nm com-pletely disappeared for PTPE 0.3F 0.7and PTPE 0.2F 0.8.How-ever,for PTPE 0.1F 0.9,the peak at 415nm remained stable even after the fraction of water arrived at 50%.Because of the relatively high content of fluorene units in PTPE 0.1F 0.9,most segments are composed of oligofluorenes or polyfluor-enes.Consequently,the PL intensity will be quenched by adding water into THF but will not disappear in the spec-trum,as shown in Figure 5(f).This indicates that AIE-char-acteristic units and ACQ-characteristic units can be copoly-merized at appropriate ratio to give fluorescent dual-channel CPs.The relationship of the net increase in PL intensity [(I ÀI 0)/I 0]with water fraction (vol %)in Figure 7shows that the PL intensity emitted from TPE segments is enhanced,whereas that emitted from fluorene segments is reduced as the water fraction increases.The best enhancement is observed for PTPE ,which has the highest TPEcontent.FIGURE 4Comparison of the measured lifetime (s )and natural lifetime (s n )of PTPE x F y in solution.。
高分子材料工程专业英语翻译全
第一单元什么是高聚物？什么是高聚物？首先，他们是合成物和大分子，而且不同于低分子化合物，譬如说普通的盐。
与低分子化合物不同的是，普通盐的分子量仅仅是58.5，而高聚物的分子量高于105，甚至大于106。
这些大分子或“高分子〞由许多小分子组成。
小分子互相结合形成大分子，大分子可以是一种或多种化合物。
举例说明，想象一组大小一样并由一样的材料制成的环。
当这些环互相连接起来，可以把形成的链看成是具有同种分子量化合物组成的高聚物。
另一方面，独特的环可以大小不同、材料不同，相连接后形成具有不同分子量化合物组成的聚合物。
许多单元相连接给予了聚合物一个名称，poly意味着“多、聚、重复〞，mer意味着“链节、基体〞〔希腊语中〕。
例如：称为丁二烯的气态化合物，分子量为54，化合将近4000次，得到分子量大约为200000被称作聚丁二烯〔合成橡胶〕的高聚物。
形成高聚物的低分子化合物称为单体。
下面简单地描绘一下形成过程：丁二烯＋丁二烯＋…＋丁二烯——→聚丁二烯〔4000次〕因此可以看到分子量仅为54的小分子物质〔单体〕如何逐渐形成分子量为200000的大分子〔高聚物〕。
本质上，正是由于聚合物的宏大的分子尺寸才使其性能不同于象苯这样的一般化合物。
例如，固态苯，在5.5℃熔融成液态苯，进一步加热，煮沸成气态苯。
与这类简单化合物明确的行为相比，像聚乙烯这样的聚合物不能在某一特定的温度快速地熔融成纯洁的液体。
而聚合物变得越来越软，最终，变成非常粘稠的聚合物熔融体。
将这种热而粘稠的聚合物熔融体进一步加热，不会转变成各种气体，但它不再是聚乙烯〔如图1.1〕。
固态苯——→液态苯——→气态苯加热，5.5℃加热，80℃固体聚乙烯——→熔化的聚乙烯——→各种分解产物-但不是聚乙烯加热加热图1.1 低分子量化合物〔苯〕和聚合物〔聚乙烯〕受热后的不同行为发现另一种不同的聚合物行为和低分子量化合物行为是关于溶解过程。
例如，让我们研究一下，将氯化钠渐渐地添加到固定量的水中。
专业英语polymer
Functionality in unsaturated systems
1. Unsaturated molecules are those that contain a carbon – carbon double bond, i.e. C=C. 2. This group is one functional group, but has a functionality of 2. 3. During addition polymerisation, the double bond opens and two reactive centres are formed. Hence, the functionality of a double bond is 2.
material must contain at least 2 functional groups.
We say the functionality of the monomer is 2.
13
Functionality
If the molecules that are reacting together have 1
What is functional group?
Functionality
In order for the reaction to take place, the starting
material(s) must contain functional groups.
In order for polymerisation to occur, the starting
In addition polymerization, unsaturated or cyclic molecules add to each other without elimination of any portion of the monomer molecule. The empirical formula of the polymer is then, of course, the same as that of the monomer.
化学专业英语-Polymer
2 Synthesis
2.1 Step-growth polymerization
（逐步聚合）
Step-growth polymerization, which is often also called condensation polymerization（缩聚） since it is 缩聚） almost exclusively concerned with condensation reaction taking place between multifunctional monomer molecules.
number of groups that have reacted number of groups present initially
The number average degr given by
xn =
x n，
number of molecules present initially number of molecules remaining after time
2.1.4 Linear step-growth polymerization system
Ester interchange reaction Salt dehydration Ring-opening polymerization
2.1.5 Non-linear step-growth polymerization system
Polymer Chemistry
Introduction to polymers Synthesis Structure and properties Characterization
1. Introduction to polymers
化学工程与工艺专业英语课后习题参考答案
学而不思则惘，思而不学则殆Key to Exercise Unit 1 Chemical Industries1.the Industrial Revolutionanic chemicals3.the contact process4.the Haber process5.synthetic polymers6.intermediates7.artificial fertilizers 8.pesticides (crop protection chemicals)9.synthetic fibers10.pharmaceutical11.research and development12.petrochemicalputers(automatic control equipment)14.capital intensiveSome Chemicals Used In Our Daily LifeUnit 2 Research and Development1.R&D2.ideas and knowledge3.process and products4.fundamental5.applied6.product development7.existing product8.pilot plant9.profitbility10.environmental impact11.energy cost 12.technical support13.process improvement14.effluent treatment15.pharmaceutical16.sufficiently pure17.Reaction18.unreacted material19.by-products20.the product specification21.Product storageUnit 3 Typical Activities of Chemical Engineers1.Mechanical2.electrical3.civil4.scale-upmercial-size6.reactors7.distillation columns8.pumps9.control and instrumentation10.mathematics11.industry12.academia13.steam 14.cooling water15.an economical16.to improve17.P&I Drawings18.Equipment Specification Sheets19.Construction20.capacity and performance21.bottlenecks22.Technical Sales23.new or improved24.engineering methods25.configurationsUnit 4 Sources of Chemicals1.inorganic chemicals2.derive from (originate from)3.petrochemical processes4.Metallic ores5.extraction process6.non-renewable resource7.renewable sources8.energy source9.fermentation process10.selective 11.raw material12.separation and purification13.food industry14.to be wetted15.Key to success16.Crushing and grinding17.Sieving18.Stirring and bubbling19.Surface active agents20.OverflowingUnit 5 Basic Chemicals 1. Ethylene 2. acetic acid 3.4. Polyvinyl acetate5. Emulsion paintUnit 6 Chlor-Alkali and Related Processes 1. Ammonia 2. ammonia absorber 3. NaCl & NH 4OH 4.5. NH 4Cl6. Rotary drier7. Light Na 2CO 3Unit 7 Ammonia, Nitric Acid and Urea 1. kinetically inert 2. some iron compounds 3. exothermic 4. conversion 5. a reasonable speed 6. lower pressures 7. higher temperatures 8.9. energy 10. steam reforming 11. carbon monoxide 12. secondary reformer 13. the shift reaction 14. methane 15. 3:1Unit 8 Petroleum Processing 1. organic chemicals 2. H:C ratios3. high temperature carbonization4. crude tar5. pyrolysis6. poor selectivity7. consumption of hydrogen8. the pilot stage9. surface and underground 10.fluidized bed 11. Biotechnology 12. sulfur speciesUnit 9 PolymersUnit 10 What Is Chemical EngineeringMicroscale (≤10-3m)●Atomic and molecular studies of catalysts●Chemical processing in the manufacture of integrated circuits●Studies of the dynamics of suspensions and microstructured fluidsMesoscale (10-3－102m)●Improving the rate and capacity of separations equipment●Design of injection molding equipment to produce car bumpers madefrom polymers●Designing feedback control systems for bioreactorsMacroscale (>10m)●Operability analysis and control system synthesis for an entire chemicalplant●Mathematical modeling of transport and chemical reactions ofcombustion-generated air pollutants●Manipulating a petroleum reservoir during enhanced oil recoverythrough remote sensing of process data, development and use of dynamicmodels of underground interactions, and selective injection of chemicalsto improve efficiency of recoveryUnit 12 What Do We Mean by Transport Phenomena?1.density2.viscosity3.tube diameter4.Reynolds5.eddiesminar flow7.turbulent flow 8.velocity fluctuations9.solid surface10.ideal fluids11.viscosity12.Prandtl13.fluid dynamicsUnit 13 Unit Operations in Chemical Engineering 1. physical 2. unit operations 3. identical 4. A. D. Little 5. fluid flow6. membrane separation7. crystallization8. filtration9. material balance 10. equilibrium stage model 11. Hydrocyclones 12. Filtration 13. Gravity 14. VaccumUnit 14 Distillation Operations 1. relative volatilities 2. contacting trays 3. reboiler4. an overhead condenser5. reflux6. plates7. packing8.9. rectifying section 10. energy-input requirement 11. overall thermodynamic efficiency 12. tray efficiencies 13. Batch operation 14. composition 15. a rectifying batch 1 < 2 < 3Unit 15 Solvent Extraction, Leaching and Adsorption 1. a liquid solvent 2. solubilities 3. leaching 4. distillation 5. extract 6. raffinate 7. countercurrent 8. a fluid 9. adsorbed phase 10. 400,000 11. original condition 12. total pressure 13. equivalent numbers 14. H + or OH –15. regenerant 16. process flow rates17. deterioration of performance 18. closely similar 19. stationary phase 20. mobile phase21. distribution coefficients 22. selective membranes 23. synthetic24. ambient temperature 25. ultrafiltration26. reverse osmosis (RO).Unit 16 Evaporation, Crystallization and Drying 1. concentrate solutions 2. solids 3. circulation 4. viscosity 5. heat sensitivity 6. heat transfer surfaces 7. the long tube8. multiple-effect evaporators 9.10. condensers 11. supersaturation 12. circulation pump 13. heat exchanger 14. swirl breaker 15. circulating pipe 16. Product17. non-condensable gasUnit 17 Chemical Reaction Engineering1.design2.optimization3.control4.unit operations (UO)5.many disciplines6.kinetics7.thermodynamics,8.fluid mechanics9.microscopic10.chemical reactions 11.more valuable products12.harmless products13.serves the needs14.the chemical reactors15.flowchart16.necessarily17.tail18.each reaction19.temperature and concentrations20.linearUnit 18 Chemical Engineering Modeling1.optimization2.mathematical equations3.time4.experiments5.greater understanding6.empirical approach7.experimental design8.differing process condition9.control systems 10.feeding strategies11.training and education12.definition of problem13.mathematical model14.numerical methods15.tabulated or graphical16.experimental datarmation1.the preliminary economics2.technological changes3.pilot-plant data4.process alternatives5.trade-offs6.Off-design7.Feedstocks 8.optimize9.plant operations10.energy11.bottlenecking12.yield and throughput13.Revamping14.new catalystUnit 19 Introduction to Process Design1. a flowsheet2.control scheme3.process manuals4.profit5.sustainable industrial activities6.waste7.health8.safety9. a reactor10.tradeoffs11.optimizations12.hierarchyUnit 20 Materials Science and Chemical Engineering1.the producing species2.nutrient medium3.fermentation step4.biomass5.biomass separation6.drying agent7.product8.water9.biological purificationUnit 21 Chemical Industry and Environment1.Atmospheric chemistry2.stratospheric ozone depletion3.acid rain4.environmentally friendly products5.biodegradable6.harmful by-product7.efficiently8.power plant emissions 9.different plastics10.recycled or disposed11.acidic waste solutionsanic components13.membrane technology14.biotechnology15.microorganisms。
有机化学英文课件chapter13
13-3
Nuclear Spin States
CH3 CH3 Si CH3
CH3 Tetramethylsilane (TMS)
• for a 1H-NMR spectrum, signals are reported by their shift from the 12 H signal in TMS
• the difference in resonance frequencies for hydrogens
in CH3Cl compared to CH3F under an applied field of 7.05T is only 360 Hz, which is 1.2 parts per million
13-6
Nuclear Spins in B0
• for 1H and 13C, only two orientations are allowed
13-7
Nuclear Spins in B0
In an applied field strength of 7.05T, which is readily available with present-day superconducting electromagnets, the difference in energy between nuclear spin states for
• the two frequencies couple, • energy is absorbed, and • the nuclear spin is flipped from spin state +1/2 (with
单体聚合的条件
technique where unsaturated monomer molecules add
on to a growing polymer chain one at a time. It can be
represented with the chemical equation:
n M
( M )n
体悬系浮粘聚度合 低
，散热与控
温容易；产
物分子量及
分子量分布
比较稳定； 后产 处物 理中 存工 在序 比少简量单分。散 剂 残留物。不
适用于离子
聚合等有无
水条件要求
的反应。
传乳热液控聚温合 容 易；可低温 下反应；链 增长速度快 ，分子量较 高；可直接 得到聚合物 乳产胶物。纯 化 分 离工序较为 复杂；产物 中往往残留 乳化剂。
在引发剂、热、光等作用下进行的聚合反应。 溶液聚合（Solution polymerization）
溶液聚合是将单体和引发剂溶于适当溶剂中进行的聚合反 应方法。 悬浮聚合（Suspension polymerization）
悬浮聚合是单体以小液滴状悬浮在水中进行的聚合，单体 中溶有引发剂，一个小液滴就相当于一个本体聚合的单元。 乳液聚合（Emulsion polymerization）
Coordination polymerization
Coordination polymerization is a form of addition
polymerization in which monomer adds to a growing
macCrlomolZeicguleler-tNharottuagh an organometallCicl active center.
高分子化学浙江大学polymer1Introduction-精选文档92页
Plastics Fibers Rubbers Coatings Adhensives Functional
General Fine
33
B. Processability
结晶
无定形
Molecules in a thermoplastic (热塑性）are held together by relatively weak intermolecular forces, so that the material softens when exposed to heat and then returns to its original condition when cooled
8
degree of polymerization 聚合度
Note that all three representations are equivalent. One usually chooses the representation that emphasizes the monomer (单体) from which the polymer was made.
* China
1970 27 4.9 5.5 38
1980 53 12 13 78
1990 107 24 23 154
2000 175(11*) 35 (6.4) 44 (0.9) 254
14
General Plastics(通用塑料)
15
Engineering plastics(工程塑料)
16
There are end groups on the chain that are different from the repeat units, but these usually represent a negligible portion of the molecule, so they are seldom drawn.
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Unit13 Polymer synthesis合成高分子Po lymers are a large class of materials consisting of many small molecules (called monomers) that can be linked together to form long chains, thus they are known as macromolecules. The picture at the top of the page is a short section of such a chain. A typical polymer may include tens of thousands of monomers. Because of their large size, polymers are classified as macromolecules.聚合物是一大类材料，它们是由被我们称为单体的小分子连接成长链构成的我们熟知的大分子构成。
在页面的顶部是一张短截面的链的图片。
一个典型的聚合物包括成千上万的单体。
聚合物因为有大的分子量而被归类为大分子。
Humans have taken advantage of the versatility of polymers for centuries in the form of oils, tars, resins, and gums. However, it was not until the industrial revolution that the modern polymer industry began to develop. In the late 1830s, Charles Goodyear succeeded in producing a useful form of natural rubber through a process known as "vulcanization." Some 40 years later, Celluloid (a hard plastic formed from nitrocellulose) was successfully commercialized. Despite these advances, progress in polymer science was slow until the 1930s, when materials such as vinyl, neoprene, polystyrene, and nylon were developed. The introduction of these revolutionary materials began an explosion in polymer research that is still going on today. 人类利用原油、焦油、树脂和树胶这样形式的多功能性的聚合物好几个世纪了。
然而,直到工业革命,现代聚合物工业才开始发展。
在19世纪30年代晚期,查尔斯·古德伊尔通过被称之为“硫化”这一过程成功制造出了有用形式的天然橡胶。
40年后,赛璐珞(硬塑料形成了从硝酸纤维素)成功地商品化生产。
尽管有这些进步高分子科学的发展依然很慢,直到1930年代如塑料、合成橡胶、聚苯乙烯、和尼龙这样的材料被研制出来才有快速的发展。
介绍的这些革命性的材料开始了一个聚合物研究热直到今天仍在进行着。
Unmatched in the diversity of their properties, polymers such as cotton, wool, rubber, Teflon(tm), and all plastics are used in nearly every industry. Natural and synthetic polymers can be produced with a wide range of stiffness, strength, heat resistance, density, and even price. With continued research into the science and applications of polymers, they are playing an ever increasing role in society. The following sections provide an introduction to the science of macromolecules.高分子材料如棉花、羊毛、橡胶、聚四氟乙烯(tm),和所有塑料，无与伦比的多样化性质使它们几乎被运用在每一个行业。
天然和合成聚合物可以以宽范围的刚度、强度、耐热性、密度、甚至价格生产出来。
通过对聚合物科学与应用的继续研究，聚合物正演变成社会里越来越多的角色。
下面的段落会提供高分子科学的介绍。
The study of polymer science begins with understanding the methods in which these materials are synthesized. Polymer synthesis is a complex procedure and can take place in a variety of ways. Addition polymerization describes the method where monomers are added one by one to an active site on the growing chain.研究聚合物前应该先了解这些材料的合成方法。
聚合物的合成是一个复杂的过程而且可以通过多种方式进行反应。
加聚反应描述的是单体从活性种位置逐个聚合在一起成链的方法。
Addition Polymerization 加聚反应The most common type of addition polymerization is free radical polymerization. A free radical is simply a molecule with an unpaired electron. The tendency for this free radical to gain an additional electron in order to form a pair makes it highly reactive so that it breaks the bond on another molecule by stealing an electron, leaving that molecule with an unpaired election (which is another free radical). Free radicals are often created by the division of a molecule (known as an initiator) into two fragments along a single bond. The following diagram shows the formation of a radical from its initiator, in this case benzoyl peroxide. 最常见的加成聚合反应是自由基聚合反应。
自由基就是一个简单分子得到未成对电子。
自由基因为有为了形成电子对高活性自由基获得一个额外的电子的趋势,所以它通过得到电子来破坏另一分子的共价键，同时拥有不成对电子的残余部分是另一种自由基。
自由基一般是由我们称作引发剂的分子断裂单键形成的两部分碎片。
下面的图用过氧甲酰的实例显示了引发剂形成自由基的过程。
The stability of a radical refers to the molecule's tendency to react with other compounds. An unstable radical will readily combine with many different molecules. However a stable radical will not easily interact with other chemical substances. The stability of free radicals can vary widely depending on the properties of the molecule. The active center is the location of the unpaired electron on the radical because this is where the reaction takes place. In free radical polymerization, the radical attacks one monomer, and the electron migrates to another part of the molecule. This newly formed radical attacks another monomer and the process is repeated. Thus the active center moves down the chain as the polymerization occurs.有稳定自由基的分子有与其他化合物反应的倾向。
不稳定自由基很容易同其他分子结合。
但是活性自由基不容易同其他化学物质互相作用。
自由基的稳定性根据分子的性质有很大的变化。
有不成对电子基团的位置是活性中心，因为这里是反应的场所。
自由基聚合是自由基攻击单体，同时把电子转移到另一部分分子上。
新形成的自由基再去攻击其他的电子并重复进行着这样的过程。
因此活性中心随着聚合反应沿着链传递下去。
There are three significant reactions that take place in addition polymerization: initiation (birth), propagation (growth), and termination (death). These separate steps are explained below. 加聚反应的进行有三个步骤：引发、增长、终止。